Process for breaking petroleum emulsions, certain oxyalkylated polyepoxide-treated amine-modified thermoplastic phenol-aldehyde resins and method of making same



United States Patent No Drawing. Application July 30, 1953,

'SerialhIo. 371,413

20 Claims. (or. 252 5344 The present invention is a continuation-in-part of our co-pending'application, Serial No. 364,504, filed June 26, 1953.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared'under controlled conditions from mineral oil, 'such as crude oil and relatively soft Waters orweak brines. Controlled emulsiiication and subsequent demulsific'ation under the conditions just mentioned are of Significant value in removing impurities, particularly inorganic salts, from pipe line oill i The present invention relates to the breaking of petroleum emulsions by the use of compounds obtained by oxyalkylating' with a polyepoxide the products obtained by condensing phenol-aldehyde resins having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule, which resins are reaction products of 2,4,6 C4-C24' aliphatic substituted phenols with a C1-C8 aldehyde, with'a basic hydroxylated polyamine having at least one secondary amino group and having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and formaldehyde followed by' reacting this product with ethylene, propylene, or butylene oxide, 'glycide, or mixtures thereof, and with the use of two moles of, the resin condensate to one mole of the polyepoxide, the polyepoxide being non-aryl, as more fully explained hereafter.

The present invention is characterized by the use of compounds derived from diglycidyl ethers which do not introduce any hydrophobe properties in its usual meaning but, in fact, are more apt'to introduce hydrophile properties. Thus, the diepoxides employed in the present invention are characterized by the fact that the divalent radical connecting the terminal epoxide radicals contains less than 5 carbon atoms in an uninterrupted chain.

The diepoxides employed in producing the compositions used in the present process are obtained from glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, diglycerol, triglycerol, and similar compounds. Such products are well known and are characterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which is part of the radical joining the epoxide groups. Of necessity such diepoxides must be nonaryl or aliphatic in character. The diglycidyl ethers of co-pending application, Serial No. 364,504, are invariably and inevitably aryl in character.

Patented Nov. 20, 1956 The diepoxides employed in the present process are usually obtainedby racting a glycol or equivalent compound, such as glycerol or di gilycerol, with epichlorohydrin and subsequently withan alkali Such diepoxides have been describedinthe literature and particularly the patent literature. See, for example, Italian Patent No. 400,973, dated August 8, 1951; see, also, British Patent 518,057., dated December 10, 1938; and U. S. Patent No. 2,070,990 dated February 16, 1937 to Groll et al. Reference is made also to U. 8. Patent 2,581,464, dated January 8, 1952, to Zech. This particular last mentioned patent describes a composition of the following general formula: i

in which x is at least 1, z varies from less than 1 to more than 1, and x and z together are at least 2 and not more than 6, and R is the residue of the polyhydric alcohol remaining after replacement of at least 2 of the hydroxyl groups thereof'with the epoxide ether groups of the above formula, and any remaining groups of the residue being free hydroxyl groups.

' It is obvious" from what is s'aid in the patent that variants can be obtained in which the halogen is replaced by a hydroxyl radical; thus, the formula would become I Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual'or'ganic solvents such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to diiferentiate from a reactant which is not soluble and might be not only insoluble but also infu'sible. Furthermore, solubility is a factor insofar that it sometimes is desirable to dilute the coinpound containing the epoxy rings before reacting with an amine condensate. In such instances, of course, the solvent selected would have to be one which is not su's ceptible to oxyalkylation as, for example, kerosene benzene, toluene, dioxane,'po ssibly various ketones, chlorinated solvents, dibutyl ether, dih'exyl ether, ethyleneglycol diethyl'ether, diethyl'eneglycol diethylether, and di methoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxyring is sometimes referred to as the oxirane ring to distinguish it'from other epoxy rings. otherwise, Will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore', Where a compound has two or more oxirane rings they will be referred to as polyepoxides. They"usually represent, of course,j1,2 epoxide'rings'or oxirane rings in the alpha-omega posi- Hereinafter the word' epoxy unless indicated,

a 3 tion; This is a departure of course, from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane- (1,2534 diepoxybutane).

It well may be that even though the previously suggested formula represents the principal component, or

components, of the resultant or reaction product de- I scribedin. the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecule weight,'have been described as complex resinous epoxides which are polyether derivatives of polyhydriccompounds containing an average of more than one epoxide group permolecule and free from functional or if derived from cyclic diglycerol the structure would or the equivalent compound whereinthe ring structure involves only 6 atoms, thus:

ci H III C C at i Commercially available compounds seem to be largely the former with comparatively small amounts, in fact, comparatively minor amounts, of the latter.

Having obtained a reactant having generally 2 epoxy rings as depicted in the next to last formula preceding, or low molal polymers thereof, it becomes obviousthe reaction can take place with any amine-modified phenol aldehyde resin by virtue of the fact that there are al- Ways present reactive hydroxyl groups which are part of the phenolic nuclei and there may be present reactive hydrogen atoms attached to a nitrogen atom, or an oxygen atom, depending on the presence of a hydroxylated group or secondary amino group.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having two oxirane rings and an amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of two moles of the amine condensate to one mole of the mayinclude .water, or for that'matter, a solution of.

in which n is a small whole number less than 10, and usually less than 4, and including 0, and R1 represents a divalent radical as previously describedbeing free from any radical having more than 4 uninterrupted carbon atoms in a single chain, and the characterization condensate is simply an abbreviation for the condensate which is described in greater 'detail subsequently.

Such intermediate product in turn also must be soluble but solubility is not limited to an organic solvent but Water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, gluconic acid, etc. In other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in the instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or crosslinking. Not only does this property serve to differentiate from instances where an insoluble material is deacid at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, parts of xylene and 20parts of methanol, or

70 parts of'xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10%of acetone.

A mere examination of the nature of the products before and after treatment with a .polyepoxide reveals that the polyepoxide'by and large introduces increased hydrophile character or, inversely, causes a decrease in hydrophobe character. However, the solubility characteristics of the final product, i. e., the product obtained by oxyalkylation with a monoepoxide, may vary all over the map. This is perfectly understandable because ethylene oxide, glycide, and to a lesser extent methyl glycide, introduce predominantly hydrophile character, or propylene oxide and more especially butylene oxide, introduce primarily hydrophobe character. A mixture of the various oxides will produce a balancing in solubility characteristics or in the hydrophobe-hydrophile character so as to be about the same as prior to oxyalkylation withv the monoepoxide. 7

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or bydrate, i. e.., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxyacetate, have sufli ciently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated 'March 7, 1950, to De Groote et al. in said patent such testfor emulsification using a water-insoluble solvent, generally are not xylene-soluble the obvious chemical equivalent ore uiv'alent chemical test'ca'n'b'e' made by simply using.

viously the same for the reasontliafth'ere will be two" phases on vigorous shaking andsurfaee a'ctiv'ity' makes its presence manifest. It is understood the reference in the hereto appended claims as to the use or" Xylene in the emulsification test includes such obvious variant.

For purpose of convenience what is-said hereinafter will be divided into seven parts:

Part 1 is concerned with the hydrophile nonarylpolyepoxid'es and particularly diepoxides employed as re actants;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation to yield the amine-modified resin;

Part 3 is concerned with appropriate basic hydroxylated polyamines which may be employed in the preparation of the herein-described amine-modified resins;

Part 4 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to reaction with polyepoxides, and particularly diepoxides;

Part5 is concerned with reactions involving the two precedingtypes of materials and examples obtained by such reaction. Generally speaking, this involves nothing more than reaction between 2 moles of a previouslyprepared amine-modified phenol-aldehyde resin condensate as described and one mole of a hydrophile polyepoxide so as to'yield a new and larger resin'molecule, or comparable product;

Part 6 is concerned with the use of a monoepoxide in oxyalkylating the products described in Part 5, preceding, i. e., those derived by means of-reaction between a' polyepoxide and an amine-modified phenol-aldehyde resin as described;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by'means of the previously described chemical compounds or reaction prod ucts.

PART I Reference is made to previous patents as illustrated In some instances the compounds are essentially 'de rivatives of etherized epichlorohydrin or methyl epichlorohydrin. Needless to say, such'compoundscan be derived from glycerol monochlorohydrin by etherization prior to ring closure. An example is illustrated in the previously mentioned Italian Patent No. 400,973:

Another type of diepoxide is diisobjitenyl dioxide as described in aforementioned U.- S. PatenuNo. 2,070,990,

dated February 16, 1937, to Groll, and is of the following formula: 1

The diepoxid's previouslydescribedmay be indicated by the following formula:

However, for practical purposesfthe only" diepoxide" available in quantities other than lalboratoryquantities is a derivative of glycerol or epichlorohydrin. This particular diepoxide is obtained from diglycerol which is largely acyclic diglycerol, and epichlorohydrin or equivalent thereof in that the'epichlorohydrin'itself may supply the" glycerol or diglycerol' radical in addition'to the epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative one could start with any one of a number of glycols or'poly-f glycols and it is more convenient'to include-as part of the terminal oxirane ring radical the oxygen atom 'that' wa derived from epichloro-hydrin or; as might be-the case, methyl epichlorohydrin.

comes:

In the above formula R1 is selected from groups-such as the following: 7

It is to be noted that in the aboveepoxides ther"'is. a complete absence of (a) arylradicalfs and :(b) radicals] in which'S or'more carbon atoms are" united injfajsinjgl'e" uninterrupted single group. R1 is inherently h'y drophile" in character as indicated by the fact that it is-fspecified that the precursory diol or polyol OHROH must be' water soluble in substantially al proportions, i. e.', watermie cible.

Stated another way, what is said previously means that a polyepoxide such as So presented the formula be-' ara's;

7 V is derived actually or theoretically, or at least derivable, from the diol HOROH, in which the oxygen-linked hydrogen atoms were replaced by Thus R(OH)11., where n represents 'a small whole number which is 2 or more must be water-soluble. Such limitation excludes polyepoxides if actually derived or theoret-i-callyderived at least, from Water-insoluble diols or water-insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbon atoms or thereabouts. 7

Referring to a compound of the type above in the formula in which R1 is C3H5(OH) it is obvious that reaction with another mole of epichlorohydrin with appropriate ring closure would produce a triepoxide or, similarly, if R happened to be CsH5(OH)OC3H5(OH), one could o tain a tetraepoxide. Actually, such procedure generally yields triepoxides, or mixtures with higher epoxides and perhaps in other instances mixtures in which diepoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free "from aryl groups and also free from any radical having 5 or more carbon atoms in an uninterrupted chain, T his particular diglycidyl ether is obtained by the use of epichlorohydrin in such .a manner that approximately 4 moles of epichlorohydrin yield one mole of the diglycidyl ether or, stated another way, it can be considered as being formed from one mole of diglycerol' and 2 moles of epichlorohydrin so as to give the appropriate diepoxide; The molecular weight'is' approximately 370 andthe number of epoxide groups per molecule are approximately 2. For this reason in the first of a series 'of subsequent examples this particular diglyc V idyl ether is used, although obviously'any of the others previously described would be just as suitable. For convenience, this diepoxide will be referred to as diglycidyl ether A. Such material corresponds in a general way to the previous formula.

Using laboratory procedure we have reacted diethyl ene-glycol with epichlorohydrin' and subsequently with alkali :so as to produce a product which, on examination, corresponded approximately to the following compound:

The molecular weight of the product was assumed to be 230 and the product was available in laboratory quantities only. For this reason, the subsequent table referring to the use of this particular diepoxide, which will be referred to as diglycidyl ether B, i in grams instead Other examples diepoxidesinvolving' a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of V combining erythritol with a carbonyl compound, such as formaldehyde or acetones so as to form the S-membe'red ring, "followed by conversion of the terminal hydroxyl groups into epoxy radicals.

See also Canadian Patent No. 672,935.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble,

water-insoluble resin polymers of a composition approximated in an idealized form by the formula OH 'OH OH (H it i O O O O I R R n R in the above formula 11 represents a small whole number varying from 1 to 6, 7, or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. 7

A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms, such as butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molol alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and non-oxygenated) will serve. See Example 90: of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must 7 be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that V is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic hydroxylated polyamine as specified, following the same idealized over simplification previously referred to,.the resultant product might be illustrated thus:

9 The basic hydroxylated amine maybe designatedthus:

RI HN In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may takeplace. For instance, 2 moles of amine may combine with one mole of" the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas: I

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, 'propionaldehyde. or butyraldehyde. The resin unit maybe exemplified thus:

0 H I" O H "I O H III O HI O R R I n R in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation productobtained appears to be described best in terms of the method of manufacture.

Resins can be made using an acid catalyst orbas-ic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a .catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence .of a small amountof afree base. The amount may be as small ,as a..200.th.of a percent and as much as a few 10ths of a percent. ,Sometim iS. moderate increase in caustic soda and caustic potash may be used. However, the most desirable. PIQCCdI-IIZG. in practically every case is to have the resin-neutral.

In preparing resins one does not ,get a. singlepolymer, i. e., one having just 3 units, :or just-4 units, or just Sp its, or just 6 units, etc. It is usually a mixture;-.for.instance,, one approximating 4 phenolicnucleiwill have some -,trim er and pentamer present. Thus, the molecular weightmay be such that it corresponds to a fractional value-for nas, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we; foundmo reason for using other than those -which-are lowestin; price and most readily available commercially. izFor pllrposes of convenience suitable-resinsme eharacterigedmthe following table:

TABLE I Mol. wt. Ex- R of resin ample R Position derived n molecule number of R trorn- (based on n+2) Phenyl Para. 3. 5 992. 5

Tertiary butyl do 3. 5 882. 5 Secondary butyl. Ortho 3. 5 882. 5 Oyclo-hexyl Para 3. 5 1, 025.5 Tertiary amyl 3. 5 959. 5 Mixed secondary 3. 5 805. 5

and tertiary amyl.

3.5 805.5 3. 5 1,036.5 3. 5 1, 190. 5 3. 5 1, 267. 5 a 5 1, 344. 5 a. 5 1, 498. a 3. 5 945.

Tertiary amyl 3. 5 1, 022. 5 Nonyl 3. 5 1, 330. 5 Tertiary butyl 3. 5 1, 071. 5

Tertiary amyl 3. 5 1,148. 5 Nony do 3.5 1,456.5 Tertiary butyl do 3. 5 1, 008.5

Tertiary aruyl 3. 5 1, 085. 5 Nonyl 3. 5 1, 393. 5 Tertiary butyl 4. 2 996. 6

Tertiary amyl do 4.2 1,083.4 Nonyl, do 4. 2 1, 430. 6 Tertiary butyl. 4. 8 1, 094. 4 4. 8 1, 189. 6 4. a 1, 570. 4 1.5 604. 0 1. 5 646. 0 1. 5 653. 0 1. 5 688.0

d0. 1.5 786.0 .d0 1.5 835.0 d0, 2.0 986.0

do- 2. 0 1, 028.0 (l0 2.0 8600 do 2. 0 636.0

PART 3 As has been pointed out, the amine herein employed as a reactant is a hydroxylated basic polya-mine and preferably a strongly basic polyarnine having at least one secondary amino radical, free from primary amino groups free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl, alicyclic, arylalkyl, or heterocyclic in character, subject of course to .the inclusion of a hydroxyl group attached to a carbon atom which, in turn in partof a monovalent or divalent radical.

Brevious reference has been made to .a number of polyamines which are satisfactory for use as reactants in the instant. condensation procedure. They canv be ob: tained by hydroxylation of low cost polyamines. The

cheapest amines available are polyethylene amines andv polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms.

Such amines are susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or ter tiary amine radical. in the case of polyamines having at least 3 nitrogen atoms or more, both terminal groups could'be. QQnverted into tertiar groups, or one terminal group could be converted into a tertiary group and the other. into a secondary amino group. In the same Way, the polyarnines canbe subjected to hydroxyalkylationby reaction with ethylene oxide, propylene oxide, glycide, etc. In some instances, depending on the structure, both types of reaction may be employed, i. e., one type to introduce a hdroxyethyl group, for example, and another type to introduce a methyl or ethyl radical.

By way of example the following formulas are in- H O C211 N propyleneN propyleneN C 211 4 O H HOCgH;

OH: H3

' Another procedure for producing suitable polyamines is a'reaction involving'first an alkyle'ne imine,'such"as ethylene imine or propylene imine, followed by an alkylene oxide, such as ethylene oxide, propylene oxide or glycide.

I What-has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary alicyclic amine, such as dibutylamine, di'oenzylamine, di'cyclohexylamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylene oxide followed by reaction with an imine Similarly,

and then the use of an alkylene oxide again. one can start with a primary amine and introduce two moles of an alkylene oxide so as to have a compound comparable to ethyl diethanolamine and react with two moles of an imine and then with two moles of ethylene oxide.

Reactions involving the same reactants previously described, i. e., a suitable secondary monoamine plus an alkylene imine plus an alkylene oxide, or a suitable monoamine plus an alkylene oxide plus an alkylene imine and plus'the second introduction of an alkylene oxide, can be applied to a variety of primary amines. In the case of primary amines one can either employ two moles of an alkylene oxide so as to convert both amino hydrogen atoms into an alkanol group, or the equivalent; or else 7 the primary amine can be converted into a secondary amine by'the alkylation reaction. .In any event, one can obtain a series of primary amines and corresponding secondary amines which are characterized by the fact that such amines include groups having repetitious ether link- 1 ages and thus introduce a definite hydrophile eifect by virtue of the ether linkage. Suitable polyether amines susceptible to conversion in the manner described include those of the formula they include such polyamines,

iii'iv hi'ch'v'z is a -"saint aha, minisei having a vame of 1 or more, and may be as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral l to 2 and m represents a number 0 to 1, with the proviso that the sum of m plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical.

- Other similar secondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondaryamines, are those of the composition 7 RO (CH2); V

I R--O 2)a as described in U. s. Patent No. 2,375,659, data Ma s} 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl,-etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohe'xylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, pro- 5' vided there is no negativegroup or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma a phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517, and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as with the statement that such presentation is an over-simplification. It was pointed out that at least one occurrence of R must include a secondary amino radical of the kind specified. Actually, if the polyamine radical contains two orrnore secondary amino groups the amine may be reactive at two different positions and thus the same amine may yield compounds in which R and R are dissimilar.

CH3\ H /GH:i

NpropyleneNpropyleneN I H C2H4OH 0 H3 C Ha In the firstof the two above formulas if the reaction in volves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than if the reaction took place at the intermediate secondary amino radical as differentiated from the terminal group. Again,

referring to the second formula above, although a termi: nal amino radical is not involved it is obvious again that one could obtain two different structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending on whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by the above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions where a large variety Certain hydroxylated polyamines which may be employed and which illustrate the appropriate type of reactant used for the instant condensation reaction may be illustrated by thefollowing additional examples:

NCEzCH2-N-C'HzCH2OH no on2oniNnoHion,-Nrton,onion on OH noorndHcnmn-onmrmrrnomdnomon 7 no CHrCHzNH-CH:

H-O CH2CH2NHCH.

no C'HzCHzNH'- n2 As is well known one can prepare ether amino alcohols of the type RO-CH2CH(OH)'NHCH2CH2 NHCHzCH (OH) CHz-OR in which R represents analkyl group varying from methyl to normal decyl, and in fact, the group may contain as many as 15., 20 or even 30 carbonatoms. See J. Org.

Chem., 17, 2 .(1952).

Over and above the specific examples which have appeared previously, attention is directed to the. fact that a number of suitable amines are included in subsequent Table 11.

PART 4 The products obtained by the herein described processes represent cogeneric mixtures which. are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, ,although it may be so illustrated in. an idealized simplification, it is difiicult to actually depict the final product of the cogeneric mixture. except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as diiferentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to C. .or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above What has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room' temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at 'a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can'use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in any oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent forthe reason that inmost cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difficult perhaps to add a solid ma terial instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In

any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is 'usedffor any subsequent reaction.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over 150 C. and employingvacuum, if required. This applies,of course, only to those circumstances where it is desirableor necessary to remove.

the solvent. Petroleum solvents, aromatic solvents,etc., can be used. The selection of Solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and'als'o on three other factors, two of which have been previously menfere as in the case of oxyalkylation? and the third factoris this, is an elfort to be made to purify the reaction mass by the usual procedure as, for example, a waterwash to remove any .unreacte'd. water-soluble polyamine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. we have found xylenethe most satisfactory solvent.

7 We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this'is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it Will at some 10w temperature, for instance to 40 but ultimately one must. employ the higher temperature in order to obtain products of the kind herein'described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding'itat thisstage for more than 3.01 4 hours atthe most. This, again, isa matter of convenience largely for one reason. 'Inheating and stirring the reaction mass there is a'tendency for Everything else being equal,

or mechanical mixture, if not eompletely soluble is cooled to at least the reaction temperature or somewhat below;

for example C. or slightly lower, provided this initial lowtemperature stage is employed. The formaldehyde is then added in a suitable form. Forreasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter ofchoice. in large scale manufacturing there may be some advantage in using a 30% solutionof formaldehyde but apparently this is not true on a small laboratory scale or pilot plant-scale. V 30% formaldehyde may tend to de- V crease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any .difliculty with formaldehyde loss control, one can usea more'dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory because even here water of reaction is formed.

formaldehyde to be lost. Thus, if the reaction can be con-, 7

V ducted at a lower temperature so as to use up part of the formaldehyde'at such lower temperature, then the V of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary-as previously pointed out but may be convenient under certain circumstances.

On the other hand, if the products are not mutually soluble then agitation should'be more vigorous for the reason that reaction probably takes place principally. at the in terfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene.- Refiuxing should be long enough to insure that the resin added, preferably in apowdered form, is completely soluble However, if the resin is prepared as such it may be adde'din solution form, just as preparation is described in aforementionedU. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resinsolution. If it is not soluble in the resin solution it maybe soluble in the aqueous formaldehyde solution. .If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as far as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C., for 4 or 5 hours, or at the most, up to 10-24 hours, we then complete the reaction by. raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phaseseparating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We. then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 C., and below 150 C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued 'until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In

other cases we haveused a slight excess of amine, and, V

' again, have not found anyparticular advantage in so a three-phase system instead of a two-phase system aldoing. Whenever feasible we have checked the completeness of'reaction in therusual ways, including the amount of water of reaction, molecular weight, and particulai'ly in some instanceshave checked whether or not the end-product showed surface-activity, particularly In light of what has been said previously little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration: V

1 7 Example 1 b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 phenolic nuclei as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding were powdered and mixed with a considerably lesser weight of xylene, to wit, 500 grams. The mixture was refluxed following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then 7 refluxing was employed until the odor of formaldehyde TABLE II Strength 0! Reac- Reac- Max.

Ex. Resin Amt., Amine used and amount iormalde- Solvent used tion tion distill.

N0. used grs. hyde soln. and amt. temp, time, temp.,

and amt. 0. hrs. C.

882 Amine A, 296 g 30%, 200' g... Xylene, 500 g--. 21-24 24 150 480 Amine A, 148 g. 37%, 81 g. Xylene, 480 g -23 27 156 633 do d0 Xylene, 610 g. 22-27 142 441 Amine B, 176 g. 100 g... Xylene, 300 g; 20-25 28 145 480 do 37%, 81 g Xylene, 425 g 23-27 34. 150 633 ..do 30%, 100 g Xylene, 500 g 25-27 30 152 882 Amine O, 324 g. 37%, 162 g.-. Xylene, 625 gm. 23-26 38 141 480 Amine C, 162 g 30%, 100 g Xylene, 315 g 20-21 25 143 do Xylene, 535 gm. 23-24 25 140 Xylene, 425 g 22-25 25 148 Xylene, 450 g. 20-21 25 158 Xylene, 525 g. 21-25 28 152 Xylene, 400 g 22-24 26 143 do. 25-27 36 144 Xylene, 500 g. 26-27 34 141 Xylene, 400 g 21-23 25 153 do 20-22 28 150 Xylene, 500 g 23-25 27 155 Xylene, 400 g 20-21 34 150 Xylene, 450 g- 20-24 36 152 Xylene, 500 g 20-22 30 148 0 ..r d0 Xylene, 400 g 20-29 24 143 Amine I, 172 gdo Xylene, 450 g 20-22 32 151 891 Amine I, 86 g 30%, g Xylene, 300 g 20-26 36 147 until solution was complete. It Was then adjusted to approximately 33 to 38 C., and 296 grams of symmetrical di(hydroxyethyl)ethylenediamine were added. The mixture was stirred vigorously and formaldehyde used was a 30% solution and the amount employed was 200 grams. it was added in a little over 3 hours. The mixture was stirred vigorously and kept within a temperature range of 33 to 48 C. for about 17 hours. At the end of this time it was refluxed using a phaseseparating trap and a small amount of aqueous distillate Withdrawn from time to time. The presence of formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within about 3 hours or thereabouts. As soon as the odor of formaldehyde was no longer particularly noticeable or detectible the phase-separating trap was set so as to eliminate part of the xylene was removed until the temperature reached approximately 150 C. or perhaps a little higher. The reaction mass was kept at this temperature for a little over 4 hours and the reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene Was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene. The residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for reaction was somewhat under 30 hours. In other examples it varied from 24 to more than 36 hours. The time can be reduced by cutting the low temperatureperiod to approximately 3 to 6 hours. Note that in Table II As to the formulas of the above amines referred to as Amine A through Amine I, inclusive, see immediately following:

. ucts.

HOCH2OHzNH-CHaCHOHOHr-NHCHzCILOH EOCH2CHzNH.CH

HO CHzCHzNH-CH HO CHzCHzNH-CH! Amine H- Amlne I CHaNHGH:

claimant-omen onmnorn PART Cognizance should be taken of one particular feature in connection with the'reaction involving the polyepoxide and the amine condensate and that is this; the aminemodified phenol-aldehyde resin condensate is invariably basic and'thus one need not add the usual catalysts which are used to promote such reactions. Generally speaking, the reaction will proceed at a satisfactory rate under suitable conditions without any catalyst at all.

Employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials such as caustic soda, caustic potash, sodium methylate, etc. Other catalyst maybe acidic in nature and are of the kind characterized by iron and tin chloride. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. If for any reason the reaction did not proceed rapidly enough with the diglycidyl ether or other analogous reactant, then a small amount of finely divided caustic soda or sodium methylate could be employed as a catalyst. The amount generally employed would be- 1% or 2%.

It goes without saying that the reaction can take place in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else'a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propyleneglycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of thesolvent depends in part on the subsequent use of the derivatives or reaction prod- If the reaction products are'tobe rendered solventfree and it is necessary that the solvent be readily removed as, for example,'by the use of vacuum distillation, thus xylene or an aromatic petroleum will serve.

Example The product was obtained by reaction between the diepoxide previously designated as diepoxide A, and condensate 2b. Condensate 2b wasderived from resin 5a. Resin 5a, in turn, was obtained from tertiary amylphenol employed was 105 grams, and the amount of 37% formaldehyde employed was 81 grams.

solvent (xylene) employed was 450 grams. All this has been described previously.

The solution of the condensate in xylene was adjusted to a 50% solution. In this particular instance, and in practically all the others which appear in the subsequent tables, the examples are characterized by the fact that no alkaline catalyst was added. The reason is, of course, that the condensate as such is strongly basic. If desired, a small amount of an alkaline catalyst could be added, such as finely powdered caustic soda, sodium methylate, etc. If such alkaline catalyst is added it may speed up the reaction but it may also cause an undesirable reaction, such as the polymerization of the diepoxide.

In any event, 128 grams of the condensate dissolved in approximately an equal weight of xylene were stirred and heated to about 105 C. 18.5 gramsof the diepoxide previously identified as diepoxide A, and dissolved in an equal weight of xylene, were added dropwise. The

' initial addition of the xylene solution carried the temperature to about 107 C. The remainder of the diepoxide was added during approximately an hours time. During this period of time the reflux temperature rose to about 122 C. The product was allowed to reflux at a temperature in the neighborhood of 130 C. using a phaseseparating trap. A small amount of xylene was removed by means of the phase-separating trap o that the temperature rose gradually to a maximum of 180 C. The mixture was refluxed at 180 C. for approximately 3% hours. Experience has indicated that this period of time was suificient to complete the reaction.

At the end of the period the xylene which had been removed during the reflux period was returned to the mixture. A small amount of material was withdrawn and the xylene evaporated on a hot plate in order to examine the physical properties. The material was a dark red viscous semi-solid. It was insoluble in water, it was insoluble in 5% gluconic acid, and it was soluble in xylene,

and particularly in a mixture of 8 0% xylene and 20% methanol. However, if the material was dissolved in an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend,

7 to De Groote.

Various examples obtained in substantially the same manner are enumerated in the following tables:

TABLE III Oon- Dlep- Time Max. Ex den- Amt, oxide Amt, Xylene, Molar of reactemp., Color and physical state No sate grs. used grs. grs. .ratio tion, C.

used j hrs.

128 A 18. 5 146. 5 2:1 4 180 Dark viscous semi-solid. 134 A 18. 5 152. 5 2:1 4 182 D0. 123 A 18. 5 141. 5 2: 1 4 186 DO. A 18. 5 148. 5 2:1 4 184 Do. 148 A 18. 5 166. 5 2:1 4. 5' 185 Do. 187 A 18.5 205. 5 2:1 4. 5 188 D0. 132 A 18. 5 150. 5 2:1 4. 5 180 D0. 152 A 18. 5 170. 5 2:1 4. 5 182 D0. 187 A 18. 5 154. 5 2:1 4. 5 180 Do. A 18. 5 163. 5 2: 1 4. 5 Do.

The amount of 7 TABLE IV Con- Diep- Time Max. Ex. den- Amt, oxide Amt, Xylene, Molar of reactem Color and physical state No. sate grs. used grs. grs. ratio tion, used hrs 128 B 11 139 2: 1 4 180 Dark viscous semi-solid. 134 B 11 145 2:1 4 178 Do. 123 B 11 134 2: 1 4 175 Do. 130 B 11 141 2: 1 4 182 Do. 148 B 11 159 2: 1 V 4 178 D0. 187 B 11 198 2: 1 5 182 D0. 132 B 11 143 2:1 4. 5 180 D0. 152 B 11 163 2:1 5 175 D0. 136 B 11 147 2: 1 5 182 Do. 145 B 11 156 2: 1 5 180 Do.

Solubility in regard to all these compounds was substantially similar to that which was described in Example 10.

TABLE V Probable Probable Resin conmol. wt. of Amt. of Amt. of number of Ex. No. densate reaction product, solvent, hydroxyls used product grs. grs. per molecule 30 TABLE VI Probable Probable Resin conmol. wt. of Amt. of Amt. of number of Ex. No. densate reaction product, solvent, hydroxyls used product grs. grs. per molecule 2 ,780 2 ,780 1 ,390 19 2 ,900 2 ,900 l ,450 19 2,680 2,680 ,340 19 2,820 2,820 1,410 19 3,180 3,185 1,595 19 3 ,960 3 ,960 l ,980 19 2 ,860 2 ,668 1 ,438 19 3 ,260 3 ,265 l ,635 19 2 ,940 2 ,943 1 ,473 24 3 ,120 3 ,120 l, 560 24 At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one or" diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethyl ether or" ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reactive by adding a small amount of initially lower boiling solvent such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepoxide, for instance 90% or 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular Weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true molecular Weight by several percent.

Previously the condensate has been depicted in a simplified form which, for convenience, may be shown thus:

(Amine) CH2 (Resin) CH2 (Amine) Following such simplification the reaction product with a polyepoxide and particularly a diepoxide, would be indicated thus:

[(Amine) CH Resin) 0 H; (Aminefl 1). can .1

[(Amine) C HflResin) C Ha(Amine)] in which D. G. E. represents a diglycidyl other as specified. If the amine happened to have more than one reactive hydrogen, as in the case of a hydroxylated amine or polyarnine, having a multiplicity of secondary amino groups it is obvious that other side reactions could take place as indicated by the following formulas:

[(Amine) CH (Amine)] [D.G.E.]

[(Amine) 0H,(Amine)] [(Resin) CH(Resin)] [(Resin) 0H,(Resin)] [(Amine) CH;(Amine)] [D.G.E.]

[(Resin)] All the above indicates the complexity of the reaction product obtained after treating the amine-modified resin condensate with a polyepoxide and particularly diepoxide as herein described.

PART 6 The preparation of the compounds or products described in Part 5, preceding, involves an oxyalkylating agent, to wit, a polyepoxide and usually a diepoxide. The procedure described in the present part is a further oxyalkylation step but involves the use of a monoepoxide or the equivalent. The principal diiference is only that while polyepoxides are invariable nonvolatile and can be reacted under a condenser, at least numerous monoepoxides and particularly ethylene oxide, propylene oxide, butylene oxide, etc., involve somewhat different operating conditions. Glycide and methylglycide react under practically the same conditions as the polyepoxides. Actually, for purpose of convenience, it is most desirable to conduct the previous reaction, i. e., the one involving the polyepoxide, in equipment such that subsequent reaction with monoepoxides may follow without interruption. For this reason considerable is said in detail as to oxyethylation, etc.

Although ethylene oxide and propylene oxide may represent less of a hazard than glycide, yet these reactants should be handled with extreme care. One suitable procedure involves the use of propylene oxide or butylcne oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the appropriate resin condensate in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the selected resin condensate dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophi'le properties are o'b tained, if not previously present to the desired degree. Indeed, hydrophile character can be reduced or balanced by use of some other oxide, such as propylene oxide or butylene oxide. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final product ample 1D, preceding' The amount of monoepoxides employed may be as high The polyepoxide-derived oxyalkylation-susceptible .com-

pound is the one previously designated as 1c. Po lyepoxidederived condensate 1c wasobtained, inturn, from condensate 2b and diepoxide A. Reference to Table II shows the composition of condensate 2b. Table II shows it, was obtained from resin 5a, Amine A and formaldehyde; 'A mine A is symmetrical di(hydroxyethyl) ethylene diamine. TableI shows that resin 5a was obtained from tertiary amylphenol and formaldehyde.

For purpose of convenience, reference herein and in the tables to the oxyalkylation-susceptible compound will be abbreviated in the table heading as .OSC; reference is to the solvent-free material since, for convenience, the amount of solvent is noted in a second column. Actually, part of the solvent may have'been present and in practically every case-was present in either the resinification process or the condensation process, or intreatment with a polyepoxide. Inany event, the amount of solvent prescut at the time of treatment with a monoepoxide is indicated, as stated, on a solvent-free basis.

14.65 pounds of the polyepoxide-derived condensate were mixed with 14.65 pounds of solvent (xylene in this series), along with one pound of finely powdered caustic soda as a catalyst. The reaction mixture was treated with 4.75 pounds of ethylene oxide. At the end of the reaction period the molal ratio of oxide to initial compound was approximately 14.65 to one, and the theoretical molecular weight was approximately 3880.

Adjustment was made in the autoclave to operate at a temperature of about 125 C. to 130 C., and at a pres sure oflO to pounds per square inch.

The time regulator was set so as to inject the oxide 'in approximately /2 hour and then continue stirring for a half hour longer, simply as a precaution to insure complete reaction. The reaction went readily and, as a matter of fact, the ethylene oxide probably could have been injected in 30 minutes instead of an hour and the subsequent timeallowed to insure completion of reaction may have been entirely unnecessary. The speed of reaction, particularly at low pressure, undoubtedly was due in a large measure to the excellent agitation and also to the comparatively high concentration of catalyst.

A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned, and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data or subsequent data, or in data reported in tabular form in subsequent Tables VII, VIII and IX.

v.The size of the autoclaveemployed was 35 gallons. In innumerable oxyalkylations we'have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a dilferent oxide.

, ExampleZD r .This' simply illustrates further 'oxyalkylation of Ex- 7 The oxyalkylation-susceptible compound 10 is the same as the one used in Example 1D,

preceding, because it is merely a continuation. In subsequent tables, such as Table VII, .the oxyalkylationsusceptible compound in the horizontal line concerned added solvent.

' Example ID at this stage. It is immaterial which designa- 7 tion is used so long as it is understood such practice is used consistently throughout the tables.

previously, to wit, only 4.75 pounds. amount of oxide at the end of the stage was 9.50 pounds, and the ratio of oxide to oxyalkylation-susceptible compound (molar basis) at the end was 43.2 to 1. The theoretical molecular weight was 4830. There was no In other words, it remained the same, that is, 14.65 pounds and there was no added catalyst. The entire procedure was substantially the same as in Example 1D, preceding. 7

In this, and in all succeeding examples, the time and pressure were the same as previously, to wit, to C., and the pressure 10 to 15 pounds. The time element was only one-half hour because considerably'less oxide was added.

Example 3D The oxyalkylation proceeded in the same manner' as Example 4D The oxyalkylation was continued and the amount of oxide added was the same as before, to wit, 4.75 pounds.

The amount of oxide added at the end of-the reaction was 19.0 pounds. There was no added solvent and no added catalyst. Conditions as far as temperature and pressure are concerned were the same as in previous examples. The time period was the same as before, to wit, 45 minutes. The reaction at this point showed 'modest, if any, tendency to slow up. The molal ratio of oxide to oxyalkylation-susceptible compound was 86.4 to 1. The theoretical molecular weight was 6730.

Example 5D The oxyalkylation was continued with the introduction of 9.5 pounds of oxide. No added solvent was introduced and likewise no added catalyst was introduced. The theoretical molecular weight at the end of the reaction was approximately 8630. The molal ratio of oxide to oxyalkylation-susceptible compound was 130 to 1. The time period was considerably longer, to wit, 2 hours.

Example 6D The same procedure was followed as in the previous examples without the addition of either more catalyst or more solvent. The amount of oxide added was the same as before, to wit, 28.5 pounds. oxide at the end of the reaction was considerable, 57.0

pounds. The time required to complete the reaction was greater than previously, to wit, 5 hours. At the end of the reaction period the ratio of oxide to oxyalkylationsusceptible compound was 260 to l, and the theoretical molecular weight was 14,300.

The same procedure as described in the previous examples was employed in connection with a number of the other condensations described previously. All these data have been presented in tabular form in Tables VII through XII.

In substantially every case a 35-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a IS-gallon autoclave and then transferred to a 25-gal1on autoclave, or at times to the 35-gallon autoclave. This is immaterial but happened In any event, the amount of ethylene oxide introduced was less than This meant the The molal ratio of oxide" The amount of to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring to Tables VII, VIII and IX, it will be noted that compounds 1D through 18D were obtainedby the use of ethylene oxide, whereas Examples 19D through 36D were obtained by the use of propylene oxide; and Examples 37D through 54D were obtained by the use of butylene oxide.

Referring now to Table VIII specifically, it will be noted that the series of examples beginning with IE were obtained, in turn, by use of both ethylene and propylene oxides, using ethylene first; in fact, using Example 4D as the oxyalkylation-susceptible compound. This applies to series 1E through 18E.

Similarly, series 19E through 36E involve the use of both propylene oxide and ethylene oxide in which the propylene oxide was used first, to wit, 19E was prepared from 24D, a compound which was initially derived by use of propylene oxide.

Similarly, Examples 375 through 54E involve the use of ethylene oxide and butylene oxide, the ethylene oxide being used first. Also, these two oxides were used in the series 55E through 72E, but in this latter instance the butylene oxide was used first and then the ethylene oxide.

Series 73E through 90E involve the use of propylene oxide and butylene oxide, butylene oxide being used first and propylene oxide being used next.

In series 1F through 18F thethree oxides were used. It will be noted in Example 1F the initial compound was 76E. Example 76E, in turn, was obtained from a compound in which butylene oxide was used initially and then propylene oxide. Thus, the oxide added in the series 1F through 6F was by use of ethylene oxide as indicated in Table IX.

Referring to Table IX, in regard to Example 19F it will be noted again that the three oxides were used and 19F was obtained from 60E. Example 60E, in turn, was obtained by using butylene oxide first and then ethylene oxide. In Example 19F and subsequent examples, such as 20F, 21F, etc., propylene oxide was added.

Tables X, XI and XII give the data in regard to the o'xyalkylation procedure as far as temperature and pressure are concerned and also give some data as to solubility of the oxyalkylated derivative in water, xylene and kerosene.

Referring to Table VII in greater detail, the data are as follows: The first column gives the example numbers, such as 1D, 2D, 3D, etc., etc.; the second column gives the oxyalkylation-susceptible compound employed which, as previously noted in the series 1D through 6D, is Example 1C, although it would be just as proper to say that in the case of 2D the oxyalkylation-susceptible compound was 2D. Actually, reference is to the parent derivative for the reason that the figure stands constant and probably leads to a more convenient presentation. Thus, the third column indicates the epoxide-derived condensate previously referred to.

The fourth column shows the amount of ethylene oxide in the mixture prior to the particular oxyethylation step. In the case of Example 1D there is no oxide used but it appears, of course, in 2D, 3D, and 4D, etc.

The fifth column can be ignored for the reason that it is concerned with propylene oxide only, and the sixth colmn can be ignored for the reason that it is concerned with butylene oxide only.

The seventh column shows the catalyst which is invariably powdered caustic soda.

The eighth column shows the amount of solvent which is xylene unless otherwise stated.

The ninth column shows the oxyalkylation-susceptible compound which in this series is the polye'poxide-de'rived condensate.

The tenth column shows the amount of ethylene oxide in at the end of the particular step.

Column eleven shows the same datafor propylene oxide and column twelve shows data for butylene oxide. For obvious reasons these can be ignored in the series 1D through 18D.

Column thirteen shows the amount of the catalyst at the end of the oxyalkylation step, and column fourteen shows the solvent at the end of the oxyalkylation step.

The fifteenth, sixteenth and seventeenth columns are concerned with molal ratio of the individual oxides to the oxyalkylation-susceptible compound. Data appears only in column fifteen for the reason, previously noted, that no butylene or propylene oxide were used in the present instance.

The theoretical molecular weight appears at the end of the table which is on the assumption, as previously noted, as to the probable molecular weight of the initial compound, and on the assumption that all oxide added during the period combined. This is susceptible to limitations that have been pointed out elsewhere, particularly in the patent literature.

Referring now to the second series of compounds in Table VII, to wit, Examples 19D through 36D, the situation is the same except that it is obvious that the oxyalkylating agent used was propylene oxide and not ethylene oxide. Thus, the fourth columnbecomes a blank and the tenth column becomes a blank and the fifteenth column becomes a blank, but column five, which previously was a blank in Table VII, Examples 1D through 18D, now carries data as to the amount of propylene oxide presentat the beginning of the reaction. Column eleven carries data as to the amount of propylene oxide present at the end of the reaction, and column sixteen carries data as to the ratio of propylene oxide to the oxyalkylation-susceptible compound. In all other instances the various headings have the same significance as previously. 7

Similarly, referring to Examples 37D through 54D in Table VII, columns four and five are blanks, columns ten and elevent are blanks, and columns fifteen and sixteen are blanks, but data appear in column six as to butylene oxide present before the particular oxyalkylation step. Column twelve gives the amount of butylene oxide present at the end of the step, and column seventeen gives the ratio of butylene oxide to oxyalkylation-susceptible compound.

Table VIII is in essence the data presented in exactly the same way except the two oxides appear, to wit, ethylene oxide and propylene oxide. This means that there are only three columns in which data does not appear, all three being concerned with the use of butylene xide. Furthermore, it shows which oxide was used first by the very fact that reference to Example 1B, in turn, refers to 2D, and also shows that ethylene oxide was present at the very first stage. Furthermore, for ease of comparison and also to be consistent, the data under Molal Ratio in regard to ethylene oxide and propylene oxide goes back to the original diepoxide-derived condensate In. This is obvious, of course, because the figures 86.4 and 50.5 coincide with the figures for 4D derived from 10 as shown in Table VII.

In Table VIII (Examples 19E through 36E) the same situation is involved except, of course, propylene oxide is used first and this, again, is perfectly apparent. Three columns only are blank, to wit, the three referring to butylene oxide. The same situation applies in examples such as 37E and subsequent examples where the two oxides used are ethylene oxide and butylene oxide, and the table makes it plain that ethylene oxide was used first. Inversely, Example 55B and subsequent examples show the use of the same two oxides but with butylene oxide being used first as shown on the table.

Example 73B and subsequent examples relate to the use of propylene oxide and butylene oxide. Examples beginning with 1F, 'Table IX, particularly 2F, 3F, etc., show the use of all three oxides so there are no blanks as in the first step of each stage where one oxide is ith ethylene oxide and then use propylene oxide, and then go back to 5 ethylene oxide; or, inversely, start w th propylene oxide, ide, and then go back to propylene in which butylene th either one of the two oxides,

d to a mixture of 28 tion, i. e., not attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start w i then use ethylene ox oxide; or, one could use a combination oxide is used along wi just mentioned, or a combination of both of them.

The same would be true in regar ethylene oxide and butylene oxide, or butylene oxide and propylene oxide.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber, or a straw gard to Examples 15 color, or even a pale straw color. The reason is primarily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even ion nee Xi and XII give opin re '27 his not believed any further explanat in regard to Table IX.

As previously pointed out certain initial runs using one oxide only, or in some instances two oxides, had to be duplicated when used subsequently for further reacinto consideration the solvent from the previous step and the alkali left from this step. previously pointed out, Tables X missing. be offered tion. -It'would beconfusing to referto too much detail in these various tables for the'reason that all the data appear in considerable detail and is such that all results can be readily shown. 7 7

Reference to solvent and amount of alkali at any 10 point takes crating data in connection with the entire series, comparable to what has been said 1D through 6D V The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables.

invariably yields a darker product than the original resin darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the Obviously, in the use of ethylene Oxide and pr pyl n 5 product. Products can be prepared in which the final oxide in combination one need not first use one oxide hter amber with a reddi h tint, Su h n Then the other, but one can I11 products can be decolorized by the use of clays, bleaching dark amber. Condensation of a nitrogenous product if xylene, adds nothing to the color but one may use a desired, the solvent'may be removed by distillation, and 20 and usually has a reddish color.- The solven employed, particularly vacuum distillation.

may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Theo. mol. wt.

000 00000000000 00 0000 00000000000 838333 91739715-l51 925 7 50505% 2 3 3 55555 3 887763001122776431 776W3N122336N3H8M99%%%9M123cunfifiwwwfl 47 6 9 2 5 om 1 5 om 1 580 11 1112 1 1 oxyalkyl.

cmpd.

oxyalkyl.

empd.

EtO to PrO to BuO to ox alkyl.

suscept. suscept. suscept.

cmpd.

in demulsification is concerned,

Solvent,

Catalyst,

Composition at end Oxides PrO, BuO lbs.

lbs.

EtO,

TABLE VII oso, lbs.

555 a 722 2 4 4 555555 1mm1MMllllllMMMMMMlMMMMMMMM Solvent, lbs.

Catalyst,

e S u s a m f .h n a e c .w a r mm o c m E 1 1 mu a av. n a 0 My H X X n 00 a t t o .5 W 0 a 3 h Wm c md u n S v m E120, PrO, B110, lbs.

Composition before Ex. No.

thus obtain what may be termed an for the reasonthat-if one adds hydrochloric acid, for

examgxle, v to neutralize --the alkalinity one -may partially .-neutralize the basic nitrogen radical also. The preferred procedure is to ignore the v presence of the yalkali A unless it is objectionable or else add a stoichiometric amount of 1 concentrated hydrochloric .acidsequalsto the-.causticssoda is somewhat more difiicult than ordinarily is the case present.

TATBLE XI Max. Max I .Solubillty Ex. tern pres Time, No. p. s. 'hrs.

Water Xylene Kerosene TABLE XII Max. Max Solubility Ex. temdm, pres Time,

No. p. 5. hrs. a

- Water Xylene Kerosene 7 10-15 Insoluble Soluble. 10-15 D0. 10-15 Do. 10-15 Insoluble.

7 10-15 Do. 10-15 Soluble. 10-15 Do. 10-15 D0. 10-15 Insoluble 10-15 a D0. 10-15 D0. 10-15 Soluble.

"10-15 'DO; 10-15 -Do.

10-16 Insoluble 10-15 Do. 10-15 D0.

-1015 Do. 10-15 Do. 10-15 Do. 10-15 7 Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 D0.

PART 7 As to the use of conventional demulsifying agents reference is made to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part -3. Everything that appears therein applies with equalforce and eifect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 6D, herein described.

Having thus described our invention, What we claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by a 3-step manufacturing method involving (1) condensation; (2) oxyalkylation with a poly-' in which Raisfa'n aliphatic hydrocarbon radical having at least 4 and not morethan-24 carbon atoms and substituted in the2',4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not fover32 carbon atoms in any radical at tached to any'amino nitrogenatorn, and with thefurther proviso marital; polyamine be free from any primary amino radical, any substituted imidazoline radical, and

any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable and oxyalkylation-susceptible; followed as a second step by (B) reacting said resin condensate with nonaryl hydrophile polyepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical.

in the vpolyepoxide, is water-soluble, said polyepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of acylationand oxyalkylationsusceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the polyepoxide, and then completing the reaction by a third step of (C) reacting said polyepoxidederived product with a monoepoxide; said monoepoxide being an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

" 2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by a 3-step manufacturing method in- 'volvi'ng 1) condensation; (2) oxyalkylation with a polyepox ide; and (3) oxyalkylation with a monoepoxide; said first step being that of (A) condensing (a) an oXyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyarnine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable and oxyalkylation-susceptible followed as a second step by (B) reacting said resin condensate with nonaryl hydrophile polyepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical in the polyepoxide, is water-soluble; said polyepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said polyepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of acylationand oxyalkylation-susceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the polyepoxide, and then completing the reaction by a third step of (C) reacting said polyepoXide-derived product with a monoepoxide; said monoepoxide being an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

,3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by a 3-step manufacturing method inepoxide; and (3) oxyalkylation with a monoepoxide;

said first step being that of (A) condensing (afan oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctionalmonohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunc tional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in'the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed as a second step by (B) reacting said resin condensate with nonaryl hydrophile diepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogenatoni' is'replaced subsequently by the radical A in the diepoxide is water-soluble; said diepoxides'being' free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; sai-d diepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of acylationand oxyalkylation-susceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2'moles of the resin condensate'to 1 mole of the diepoxide, and then completing the reaction by a third steps of (C) reacting said diepoxide-derived product with a monoepoxide; said monoepoxide being an alpha-beta alkylene oxide having not more than 4' carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

4. The process of claim 3 wherein the diepoxide con tains at least one reactive hydroxyl radical.

5. A process for breaking petroleum emulsions of the Water-in-oil type characterized by subjecting the emulsion to the action ofa demulsifier, said demulsifier being obtained by a 3-step manufacturing method involving- (1) condensation; (2) oxyalkylation' withffa diepoxide,

, stantial absencegof tr ifunctional phenols;

and (3) oxyalkylation with a monoepoxide; said first step being that inf-(A) condensingw) an oxyalkylationsusceptible fusible, non-oxygenated organic solventsoluble, 'waterrinso'luble, low -stage phenol-aldehyde resin' having an vaverage molecular weight corresponding to at least 3 and not over 6' phenolic nuclei per resin molecule; said resin being difunctionalionly in regard to r'neth:

ylQl-forming; reactivity; said resin being derived by re.-

action between. a difunctionalmonohydric phenol and an aldehyde havinggnotrover. fit-carbon atoms andvreactive toward; said phenol; saidtresin, being formed inv-thesubbeing ofthe formula in which R isfan aiiphaticzhydrocarbon radical having atleast 4 'and-not more than '24 carbon; atoms and'sub V stituted; in the 2,4,6 position; (b) a basic hydroxylated 7 oust condensation product resulting from the process be heat-stable and oityalkylation-susceptible; followed as a fsecond step by (B)Ireacting said resin condensate with a 'hydroxylated diepoxypolyglycerol having not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B)' be members of the class 7 consisting of non-thermosetting solvent-soluble liquids and low-meltingsolidsy'with the added proviso that the reaction product be a member of the class of acylation and oxyalkylation-susceptible' solvent-soluble liquids and; low-melting solids; and said reaction between (A) and (B) being conductedsbelow the pyrolytic point said phenol .11; The process of claim 1 withtthe proviso that hydrophile properties ofthe product :offthe condensation reaction employed in the. form of-amernber of the class consistingror" (a) the anhydrobase asis, (:b): the free :base

and (c) the salt of gluconic acid, in :anequal weight of xylene are sufficient to produce an emulsionxwhen said Xylene'solution is shaken vigorouslywithl to 3' volumes of Water. t v t q t 12. The process of 'claimu2 with: the proviso :that the hydrophile propertiesof the product of the condensation 7 reaction employed in thesformgot-a Ineinber:ofthe,.,clasfs consisting of (a) ztheaanhydro vbaseas; is li)".the-free base, and (c) the salt of gluconic acid, in an equal Weight ofxylene aresufficient to produce an emulsion when said'xylene solution is shaken vigorously with 1 to 3 volumes of water. t

13. The process of claim 3 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting-of (a)=the:'anhydro base asis'tb 1the freeibase;

and (c) the salt .offgluconic acid intan equal weight of xylene are sufiicient to produce an emulsion whens-said 'xylene solution'is shaken vigorously with l to 3 volumes of water.

14. The process of claim 4 with the proviso that the hydrophile properties of the product of the condensation of the reactants andlthe resultan'ts of reaction; andwith the-final provso thattthe ratio'of reactants-be 2-moles' of the. resin condensate to 1 mole of the diepoxide; and then completing the reaction 'byua third step of (C) reacting said di epoxiderde'rived product with .a monoenpoxide;

said monoepoxide being an alpha-beta alkylene oxide' having not more than 4 carbon'atoms and selected from the class consisting of ethylene oxide, propylene oxide,

butylene orlide, glycide and methylglycide.

' "6."Thefprocess' of claim SWherein the 'polyglycerol derivative has not over 5 glycerol nuclei. a 7. The'process of claim 5 wherein the'polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted. a t t SJThe process of claim'5 wherein the polyglycerol dev rivativelhasnot over, 5' glycerol'nuclei, and the precusory' phenol isfpara-substituted and contains at least 4 and not over l4'carbon atoms in the substituent group.

f 9.'*The process of'claim .5 wherein the polyglycerol derivativethas notover 5 glycerol nuclei, and the precursory'phenol' is'para-substituted and contains at least 4 and'not ove'r' l4' carbon atoms'in'the'substituent group,

and the'precur'sory aldehyde isformaldehyde.

110. The process of ,claiinS wherein'the"polyglycerol fderivative has 'noto ver' 5 glycerol nuclei, and the precu ory"pheuol is para-substituted and contains at least ndnot 14'c'arbon atoms in the substituent group, and th precursoryfaldehyde is'iorr'naldehyde, and the total b er phenolic nuclei in the initial resin is not over 5.

*reactionemployed in the formtof a'memberzof 'the'class consisting of (a) the anhydro base as is (:b) thelfreeibase;

and (c) the salt of gluconic acid, in:an equal weight'of xylene arev sufficient to produce an emulsion when said V 'xylene solution is shaken vigorously with 'lto 3 volumes t of water. e a 15. The process of claim 5 with theproviso that the hydrophile properties of the productao-f the condensation reaction employed in theform of' a member of the class consisting of (a') the anhydro base as-is' (b) the'free base, and (c) the salt of gluconic acid,in-an-equal weight of; xylene are sufiicienttoproduce an emulsion when said xylene solution is shaken vigorously with lito 3 volumes of water. 7 V in V '16. The process of claim 6-with the proviso that the hydrophile properties of the: product of the condensation reaction employed in the form of a member of the class consisting :of (a) the anhydro base as is (b) the free base,

and (c) the, salt of'gluconi'c acid, inan equal weightof Xylene are sufiicient to produce an emulsion when said Xylene solution is shaken vigorously with 1 m3 volumes V of water. e

17. The process ofclaim 7 with theproviso thatithei hydrophile properties of the product of the co'nden's-ation ,reaction employedin the form of atmember of the class consisting'of (a) the anhydro base as is (b) the free base,

and (c) the salt of'gluconic acid, in an equal weighte'of'v e xylene are suificient to produce, an emulsion whenzsaid xylene solution is shaken vigorously with 1 to 3volu nes of Water t 18. The process of claimfli iwith the provisothat. the i hydrophile properties of the, product of the condensation reaction employed in the form of a member :ofvthecla'ss consisting of (a) the anhydro base as is, ,(b) the free base, and (c) the salt of gluconicacid, in an equal Weight of Xylene are isufficient to produce an emulsion 'lwhen said I xylene solution is shaken vigorously with 1 'to"3 volumes of water.

19 The process of claim 9 with the proviso that'the 1 hydrophile properties of the productof the'condensation reaction employed in the form of a memberofthe'class consisting of (a) the anhydro base "as is (b) the freebase', and (c )tthesalt of gluconic acid, in anfequal weight of xylene are sutficient'to'produce anemulsion when said shaken vigorously withl .to 3 volumes I xylene solution is of water.

20. The processfof claim "10 with the proviso thatjthe hydrophile properties of the product of' the condensation 

1. A PROCESS FOR BREAKING PETROLUMN EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION OF THE ACTION OF A DEMULSIFIER, SAID DEMULSIFIER BEING OBTAINED BY A 3-STEP MANUFACTURING METHOD INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A POLYEPOXIDE; AND (3) OXYALKYLATION WITH A MONOEPOXIDE; SAID FIRST STEP BEING THAT OF (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOLALDEHYDE RESIN HAVING AN AVEAGE MOLECUALR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 